The invention relates to new bi- and polyfunctional reactive dyestuffs, their preparation and their use.
Although bifunctional reactive dyestuffs are known, for example, from DE-A-2 614 550, EP-A-70 807, EP-A-70 806 and EP-A-74 928 and tri- and tetrafunctional reactive dyestuffs are known, for example, from EP-A-395 951, the known reactive dyestuffs still have diverse disadvantages in terms of their use, for example too low a fixing yield.
The present invention relates to new reactive dyestuffs of the formula 
wherein
D is the radical of an organic dyestuff from the monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone or the nitroaryl series,
W denotes a direct bond or bridge member, in particular represents a direct bond,
R1 denotes H or C1-C4-alkyl, which can be substituted, for example, by OR, OSO3H, SO3H, COOH or halogen,
R represents H, CH3 or C2H5,
R2 denotes C1-C4-alkyl, in particular methyl,
Z represents xe2x80x94CH2xe2x80x94CH2xe2x80x94OSO3H or xe2x80x94CHxe2x95x90CH2,
X represents F, Cl or Br and
n denotes 1 or 2.
The following statements apply to the alkyl, aryl, aralkyl, hetaryl, alkoxy, halogen and acylamino radicals mentioned in the present Application and to the bridge members:
Alkyl groups are understood as meaning, in particular, those having 1 to 4 C atoms, which can optionally contain substituents, for example halogen, such as Cl or Br, OH, CN, CO2H, SO3H or OSO3H.
Alkoxy radicals are understood as meaning, in particular, those having 1 to 4 C atoms.
Halogen is understood as meaning, in particular, chlorine or fluorine.
Acylamino radicals are understood as meaning, in particular, those having 1 to 4 C atoms, such as formylamino, acetylamino, propionylamino and n-butyrylamino.
Suitable bridge members W are, for example: 
wherein Rw represents hydrogen or alkyl, and Alkylene denotes an alkylene radical having 1 to 6 C atoms, where * identifies the atom or group bonded to the chromophore D.
Alkylene radicals which may be mentioned are: 
The invention furthermore relates to the preparation of the reactive dyestuffs of the formula (I):
a) either by condensation of dyestuffs of the formula 
wherein
D, W, R1 and n have the abovementioned meaning, with n moles of trihalogenotriazines of the formula 
xe2x80x83to give compounds of the formula 
xe2x80x83and further condensation of the compounds of the formula (IV) with n moles of the components of the formula
R2xe2x80x94NHxe2x80x94CH2CH2xe2x80x94SO2xe2x80x94Zxe2x80x83xe2x80x83(V),
wherein
R2 and Z have the abovementioned meaning, or
b) in the reverse sequence, by condensation of trihalogenotriazines of the formula (III) with the components of the formula (V) to give the primary condensation products 
wherein
R2 and Z have the abovementioned meaning, and further condensation of n moles of the compounds of the formula (VI) with the dyestuffs of the formula (II) or
c) by condensation of suitable precursors with the trihalogenotriazines (III) and the components of the formula (V) or by condensation of suitable precursors with the primary condensation products of the formula (VI) and subsequent dyestuff synthesis.
The invention furthermore relates to a process for the preparation of compounds of the formula (V), characterized in that compounds of the formula
R2xe2x80x94NHxe2x80x94C2H4xe2x80x94Sxe2x80x94C2H4xe2x80x94OH,
which are obtained by reaction of 3-alkyl-2-oxo-oxazolidinones of the general formula 
with 2-mercaptoethanol, are converted by oxidation, in particular with H2O2, into compounds of the formula
R2xe2x80x94NHxe2x80x94C2H4xe2x80x94SO2xe2x80x94C2H4xe2x80x94OH
and these are then converted into compounds of the general formula (V) in the customary manner.
The condensations of the starting components with the trihalogenotriazines are carried out in aqueous or organic-aqueous media in the presence of acid-binding agents, regardless of the sequence. Depending on the nature of the starting components, the first stage of the condensation is carried out here in pH ranges of 2 to 8, preferably 3 to 7, and at temperatures of 0 to 40xc2x0 C., preferably 0 to 25xc2x0 C. Replacement of the second halogen atom of the triazine takes place in the pH range from 4 to 10, preferably 5 to 9, and in the temperature range from 0 to 60xc2x0 C., preferably 0 to 30xc2x0 C.
Acid-binding agents are, for example, carbonates, hydroxides or phosphates, such as sodium carbonate, sodium bicarbonate, dilute sodium hydroxide solution, di- or trisodium phosphate or sodium fluoride.
If the condensation or the dyestuff synthesis is to lead directly to a dyestuff solution or to a liquid dyestuff preparation, it may be advantageous to use lithium carbonates or lithium hydroxide, if appropriate together with solubilizing agents and/or stabilizing buffer systems. Other conversion reactions of the dyestuffs or precursors thereof, such as metallization reactions, sulphonations or introduction of acylamino groupings, can in general be carried out at any desired stages of the dyestuff syntheses.
Particularly useful dyestuffs from the anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone or nitroaryl series are water-soluble formazan, anthraquinone and phthalocyanine dyestuffs, and in particular those which contain sulphonic acid and/or carboxylic acid groups. The dyestuffs can be either metal-free or metal-containing, the copper, nickel, chromium and cobalt complexes being of preferred interest under the metal complexes.
Suitable dyestuff radicals D of this class or the dyestuffs containing amino groups on which the dyestuffs of the formula (I) are based are described in a very large number in the literature. Examples which may be mentioned here are:
EP-A 54 515, EP-A 69 703, EP-A 70 807, DE-3 222 726,
DE-A 2 650 555, DE-A 3 023 855, DE-A 2 847 938,
DE-A 2 817 780, GB-A 2 057 479, DE-A 2 916 715,
DE-A 2 814 206, DE-A 3 019 936, EP-A 45 488 and
Venkataraman: The Chemistry of Synthetic Dyes, Volume VI, Chapter II, pages 211-325, New York, London; 1972.
A radical which contains one or more groups which confer water-solubility, in particular sulpho groups, but no further fibre-reactive radicals being a particularly suitable radical of an organic dyestuff of this class.
Preferred dyestuffs are those of the following formula (1) to (8), wherein, in general, Bxe2x80x2 comprises a radical of the formula 
and R1, X, R2 and Z have the abovementioned meaning 
wherein
R3=H, methyl, methoxy or chlorine
R4=H or SO3H and
R5=H, methyl or ethyl 
xe2x80x83wherein
B denotes a radical of the formula 
xe2x80x83in which the substituents X, R2 and Z have the above-mentioned meaning, and 
xe2x80x83wherein
A represents an optionally substituted phenylene or an optionally substituted aromatic-aliphatic bridge member, or represents a straight-chain or branched C1-C6-alkylene which is optionally interrupted by groupings containing heteroatoms, such as NR6, O or S, and can be substituted by C1-C6-alkoxy, OSO3H, SO3H, COOR or halogen,
and wherein, within a bridge member A, the group NR6 can also form a heterocyclic aliphatic ring with the group NR1, in particular 
T1 and T2=independently of one another H, Cl, Br, C1-C2-alkyl, OCH3, OC2H5, acylamino, C1-C2-alkoxycarbonyl,
R6 and R7=independently of one another H or C1-C4-alkyl, which can be substituted by OR, OSO3H, SO3H, COOR or halogen,
R=H, CH3 or C2H5. 
wherein
Me=Cu or Ni,
Pc=the radical of a phthalocyanine,
u+v+w=3.4-4.0, with the proviso that
u=0.8-2.0,
v=0-1.0 and
w=1.0-3.0, and
A has the abovementioned meaning,
R7 has the abovementioned meaning,
R8 and R9=H or C1-C2-alkyl, which is optionally substituted by OH, OSO3H, SO3H or COOH. 
wherein
v1 and w1=0 or 1, where w1 is not identical to v1,
R10 and R11 independently of one another are H, C1-C4-alkyl, C1-C4-alkoxy, OH, halogen, COOH, NO2, SO3H, sulphonamido, C1-C4-alkylcarbonylamino, optionally substituted phenylcarbonylamino, C1-C4-alkylsulphonylamino or optionally substituted phenylsulphonylamino.
Other particularly useful dyestuffs of this series are water-soluble azo dyestuffs, and in particular those which contain sulphonic acid and/or carboxylic acid groups. The dyestuffs can be either metal-free or metal-containing, the copper, nickel, chromium and cobalt complexes being of preferred interest among the metal complexes.
Suitable dyestuff radicals D or the dyestuffs of this class containing amino groups on which the dyestuffs of the formula (I) are based are described in a very large number in the literature. Examples which may be mentioned here are:
EP-A 54 515, EP-A 69 703, EP-A 70 807, EP-A 497 174,
DE-3 222 726, DE-A 2 650 555, DE-A 3 023 855,
DE-A 2 847 938, DE-A 2 817 780, GB-A 2 057 479,
DE-A 2 916 715, DE-A 2 814 206, DE-A 3 019 936,
EP-A 45 488 and Venkataraman: The Chemistry of Synthetic Dyes, Volume VI, Chapter II, pages 211-325, New York, London; 1972.
Preferred radicals of an organic azo dyestuff correspond, for example, to the following groups
Dixe2x80x94Nxe2x95x90Nxe2x80x94(Mxe2x80x94Nxe2x95x90N)0 or 1Kxe2x80x94
xe2x80x94Dixe2x80x94Nxe2x95x90Nxe2x80x94(Mxe2x80x94Nxe2x95x90N)0 or 1K
xe2x80x94Dixe2x80x94Nxe2x95x90Nxe2x80x94(Mxe2x80x94Nxe2x95x90N)0 or 1Kxe2x80x94
Di represents the radical of a diazo component of the benzene or naphthalene series which is optionally substituted by substituents customary in azo chemistry, in particular hydroxyl, methyl, ethyl, methoxy or ethoxy groups, optionally substituted alkanoylamino groups having 2-4 C atoms, optionally substituted benzoylamino groups or halogen atoms and SO2xe2x80x94Z,
K represents the radical of a coupling component of the benzene, naphthalene or ketomethylene series which is optionally substituted by substituents customary in azo chemistry, in particular hydroxyl, amino, methyl, ethyl, methoxy or ethoxy groups, optionally substituted alkanoylamino groups having 2-4 C atoms, optionally substituted benzoylamino groups or halogen atoms,
M represents the radical of a middle component of the benzene or naphthalene series which is optionally substituted by substituents customary in azo chemistry, in particular hydroxyl, methyl, ethyl, methoxy or ethoxy groups, optionally substituted alkanoylamino groups having 2-4 C atoms, optionally substituted benzoylamino groups.or halogen atoms, and
Di, M and K together contain at least two sulphonic acid groups, preferably three to four sulphonic acid groups.
Important azo dyestuffs are, for example, those of the benzene-azo-naphthalene series, the bis-(benzene-azo)-naphthalene series, the benzene-azo-5-pyrazolone series, the benzene-azo-benzene series, the naphthalene-azo-benzene series, the benzene-azo-aminonaphthalene series, the naphthalene-azo-naphthalene series, the naphthalene-azo-5-pyrazolone series, the benzene-azo-pyridone series, the benzene-azo-aminopyridine series, the naphthalene-azo-pyridone series, the naphthalene-azo-amino-pyridine series and the stilbene-azo-benzene series, the dyestuffs containing sulphonic acid groups also being preferred here. In the case of metal complex azo dyestuffs, the metal complex-bonded groups are preferably in the o-position relative to the azo group, for example in the form of o,oxe2x80x2-dihydroxy-, o-hydroxy-oxe2x80x2-carboxy-, o-carboxy-oxe2x80x2-amino- and o-hydroxy-oxe2x80x2-amino-azo groupings.
Preferred dyestuffs are those of the following formulae (9) to (50), wherein, in general, B comprises a radical of the formula 
and X, R2 and Z have the meaning given under formula (I): 
dyestuffs and dyestuffs capable of forming metal complexes of the formulae (20) to (50): 
Cu (1:1 complex) or Cr and Co (1:2 complex) are the preferred metal atom. Cr and Co complexes can contain the azo compound of the abovementioned formula once or twice, that is to say they can be built up symmetrically or unsymmetrically with any other desired ligand groups. 
wherein
acyl is, for example, acetyl or optionally substituted benzoyl,
R17=H or C1-C2-alkyl, optionally substituted by SO3H or NH2,
R1=H, CH3 or C2H5,
R19=H or sulpho,
R13=H, CH3, OCH3 or Cl,
R12=H, C1-C4-alkyl, C1-C4-alkoxy, Cl, Br, COOH or SO3H,
R14=H, OH, NH2, NHCOCH3, NHCOPh, Cl, C1-C4-alkoxy or C1-C4-alkyl,
R16=H, SO3H, CH2SO3H, Cl, C1-C4-alkylsulphonyl, CN or carboxamide, in particular CONH2,
R15=H, C1-C4-alkyl, C1-C4-alkoxy, Cl, Br or acylamino, in particular C1-C4-alkylcarbonylamino or arylcarbonylamino, such as optionally substituted phenyl carbonylamino, C1-C4-alkylsulphonylamino, amino carbonylamino, C1-C4-alkylsulphonylamino or arylsulphonylamino,
R18=H, C1-C4-alkyl, C1-C4-alkoxy, OH or SO3H.
The fused rings indicated by broken lines represent alternatively possible naphthalene systems.
Preferred reactive dyestuffs are furthermore those of the formula (I)
wherein
the radical D, preferably a radical of an organic dyestuff from the monoazo or polyazo series, is substituted once or twice by the group
xe2x80x83Zxe2x80x2xe2x80x94O2Sxe2x80x94(CH2)0-1xe2x80x94
wherein
Zxe2x80x2 denotes xe2x80x94CHxe2x95x90CH2, xe2x80x94CH2xe2x80x94CH2xe2x80x94OSO3H, xe2x80x94CH2xe2x80x94CH2xe2x80x94Cl, xe2x80x94CH2xe2x80x94CH2xe2x80x94Br, xe2x80x94CH2xe2x80x94CH2xe2x80x94S2O3H, xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94COxe2x80x94CH3, xe2x80x94CH2xe2x80x94CH2xe2x80x94OPO3H2 or xe2x80x94CH2xe2x80x94CH2xe2x80x94OH.
Particularly preferred reactive dyestuffs of the formula (I) are those
wherein
the radical D, preferably a radical of an organic dyestuff from the monoazo or polyazo series, is substituted once or twice by the group
Zxe2x80x2xe2x80x94O2Sxe2x80x94(CH2)0-1xe2x80x94
wherein
Zxe2x80x2 has the above meaning and n=1.
Reactive dyestuffs of the formula (I) which are furthermore particularly preferred are those in which
n=1,
W=a direct bond and
D is a radical of the general formula (IX) 
wherein
R20 denotes H, C1-C4-alkyl, C1-C4-alkoxy, Cl, Br, acylamino, in particular C1-C4-alkylcarbonylamino or arylcarbonylamino, such as optionally substituted phenylcarbonylamino, C1-C4-alkyl-sulphonylamino, amimocarbonylamino, C1-C4-alkyl-sulphonylamino or arylsulphonylamino,
R21 denotes H, C1-C4-alkyl, Cl, Br, C1-C4-alkoxy or COOH,
R22 denotes H, C1-C4-alkyl, C1-C4-alkoxy, SO3H, Cl or Br,
K denotes a bivalent radical of the general formulae (Xa)-(Xd) 
xe2x80x83and where the bonds identified with * are bonded to the group xe2x80x94NR1xe2x80x94B. B has the meaning of formula (VIa).
Zxe2x80x2 particularly preferably denotes xe2x80x94CHxe2x95x90CH2 or xe2x80x94C2H4xe2x80x94OSO3H.
Suitable diazo components, on which the radicals D of the formula (IX) are based, for the dyestuffs of the formulae (I) are, for example:
aniline-4-xcex2-sulphatoethylsulphone,
aniline-4-xcex2-thiosulphatoethylsulphone,
aniline-4-vinylsulphone,
aniline-3-xcex2-sulphatoethylsulphone,
aniline-3-vinylsulphone,
2-methoxy-aniline-5-xcex2-sulphatoethylsulphone,
2-methoxy-aniline-5-xcex2-thiosulphatoethylsulphone,
2-methoxyaniline-5-vinylsulphone,
4-methoxy-aniline-3-xcex2-sulphatoethylsulphone,
4-methoxy-aniline-3-xcex2-vinylsulphone,
2,5-dimethoxyaniline-4-xcex2-sulphatoethylsulphone,
2,5-dimethoxy-aniline-4-vinylsulphone,
2-methoxy-5-methyl-aniline-4-xcex2-sulphatoethylsulphone,
aniline-2-xcex2-sulphatoethylsulphone,
3-(3- or 4-aminobenzoyl)-aminophenyl-xcex2-sulphatoethyl-sulphone,
2-methoxy-5-methyl-aniline-4-vinylsulphone,
6-carboxy-aniline-3-xcex2-sulphatoethylsulphone,
6-carboxyaniline-3-vinylsulphone,
2-sulphoaniline-4-xcex2-sulphatoethylsulphone,
2-sulphoaniline-4-vinylsulphone,
2,4-disulphoaniline-5-vinylsulphone,
2-naphthylamine-8-xcex2-sulphatoethylsulphone,
2-naphthylamine-6-xcex2-sulphatoethylsulphone,
1-sulpho-2-naphthylamine-6-xcex2-sulphatoethylsulphone,
1-naphthylamine-4-xcex2-sulphatoethylsulphone,
1-sulpho-2-naphthylamine-5-xcex2-sulphatoethylsulphone,
6-sulpho-2-naphthylamine-8-xcex2-sulphatoethylsulphone,
2-amino-3-sulpho-naphthalene-6,8-bis (xcex2-sulphatoethyl-sulphone),
1-naphthylamine-5-xcex2-sulphatoethylsulphone,
2-naphthylamine-5-xcex2-sulphatoethylsulphone,
2-naphthylamine-8-xcex2-suphatoethylsulphone,
8-sulpho-2-naphthylamine-6-xcex2-sulphatoethylsulphone,
4-aminobenzyl-xcex2-sulphatoethylsulphone,
3-aminobenzyl-xcex2-sulphatoethylsulphone,
4-aminobenzylvinylsulphone,
3-aminobenzylvinylsulphone,
3-amino-4-sulphobenzyl-xcex2-sulphatoethylsulphone,
4-amino-3-sulphobenzylvinylsulphone,
2xe2x80x2-(xcex2-sulphatoethylsulphonyl)-3-sulpho-4-aminoazobenzene,
3xe2x80x2-(xcex2-sulphatoethylsulphonyl)-3-sulpho-4-aminoazobenzene,
4xe2x80x2-methoxy-3xe2x80x2-(xcex2-sulphatoethylsulphone)-3-sulpho-4-aminoazobenzene,
4xe2x80x2-vinylsulphonyl-2xe2x80x2,3-disulpho-4-aminoazobenzene,
2xe2x80x2-(xcex2-sulphatoethylsulphonyl)-6-methyl-3-sulpho-4-amino-azobenzene,
3xe2x80x2-(xcex2-sulphatoethylsulphonyl)-6-methyl-3-sulpho-4-amino-azobenzene,
4xe2x80x2-(xcex2-sulphatoethylsulphonyl)-6-methyl-3-sulpho-4-amino-azobenzene,
4xe2x80x2-(xcex2-sulphatoethylsulphonyl)-2,6-dimethyl-3-sulpho-4-aminoazobenzene,
3xe2x80x2-(xcex2-sulphatoethylsulphonyl)-6-methoxy-3-sulpho-4-aminoazobenzene,
3xe2x80x2,4xe2x80x2-bis-(xcex2-sulphatoethylsulphonyl)-6-methoxy-3-sulpho-4-aminoazobenzene,
4xe2x80x2-(xcex2-sulphatoethylsulphonyl)-6-methoxy-3-sulpho-4-aminoazobenzene,
4xe2x80x2-(xcex2-sulphatoethylsulphonyl)-2-methyl-5-methoxy-3-sulpho-4-aminoazobenzene,
4xe2x80x2-(xcex2-sulphatoethylsulphonyl)-2,5-dimethoxy-3-sulpho-4-aminoazobenzene,
3xe2x80x2-(xcex2-sulphatoethylsulphonyl)-2,5-dimethoxy-3-sulpho-4-aminoazobenzene,
2-(4xe2x80x2-amino-3xe2x80x2-sulphophenylazo)-6-(xcex2-sulphatoethylsulphonyl)-naphthalene,
2-(4xe2x80x2-amino-6xe2x80x2-methyl-3xe2x80x2-sulphophenylazo)-1-sulpho-6-(xcex2-sulphatoethylsulphonyl)-naphthalene,
2-(4xe2x80x2-amino-6xe2x80x2-methyl-3xe2x80x2-sulphophenylazo)-6-(xcex2-sulphatoethylsulphonyl)-naphthalene,
2-(4xe2x80x2-amino-3xe2x80x2-sulphophenylazo)-8-sulpho-6-(xcex2-sulphatoethylsulphonyl)-naphthalene,
2-(4xe2x80x2-amino-6xe2x80x2-methyl-3xe2x80x2-sulphophenylazo)-1,7-disulpho-5-(xcex2-sulphatoethylsulphonyl)-naphthalene.
Suitable coupling components H-K-NHR1 on which the radicals K are based are, for example: 
where * marks the coupling site and m and p represent the meta- and para-position of the amino group relative to the azo group.
Preferred dyestuffs in the context of formula I: with a dyestuff radical D of the formula (IX) are those of the following formulae (51) to (60), wherein, in general, B comprises a radical of the formula 
and X, R2 and Z have the abovementioned meaning: 
wherein
R1=H, CH3 or C2H5,
R20=H, C1-C4-alkyl, C1-C4-alkoxy, Cl, Br, acylamino, in particular C1-C4-alkylcarbonylamino or arylcarbonylamino, such as optionally substituted phenylcarbonylamino, C1-C4-alkylsulphonylamino, aminocarbonylamino, Cl-C4-alkylsulphonylamino or arylsulphonylamino,
R21=H, C1-C4-alkyl, C1-C4-alkoxy, Cl, Br or COOH,
R22=H, C1-C4-alkyl, C1-C4-alkoxy, Cl, Br or SO3H.
Dyestuffs of this series which are likewise particularly useful are reactive dyestuffs of the formula 
DK=the radical of a diazo component of the benzene or naphthalene series,
KK=the radical of a coupling component of the formula 
xe2x80x83wherein the radical of the formula XII and the azo group are linked to one another via the bond marked with *,
B=a radical of the formula 
Y=a heterocyclic fibre-reactive radical which differs from B,
R0 and R1=independently of one another H or C1-C6-alkyl which is optionally substituted with substituents such as, for example, OH, COOH, SO3H or OSO3H,
and R2, X and Z have the above meaning.
Suitable fibre-reactive radicals Y, that is to say those which react with the OH or NH groups of fibres under dyeing conditions to form covalent bonds, are preferably those which contain at least one reactive substituent bonded to a 5- or 6-membered aromatic-heterocyclic ring, for example to a monoazine, diazine or triazine ring, in particular a pyridine, pyrimidine, pyridazine, thiazine, oxazine or asymmetric or symmetric triazine ring, or to such a ring system which contains one or more fused-on aromatic-carbocyclic rings, for example a quinoline, phthalazine, cinnoline, quinazoline, quinoxaline, acridine, phenazine or phenanthridine ring system, and which are not bonded to a further chromophore.
Reactive substituents on the heterocyclic ring which may be mentioned are, for example, halogen (Cl, Br or F), ammonium, including hydrazinium, pyridinium, picolinium, carboxypyridinium, sulphonium, sulphonyl, azido(N3), thiocyanato, thioether, oxy-ether, sulphinic acid and sulphonic acid.
Specifically, for example, the following radicals may be mentioned for Y:
2,4-Difluorotriazin-6-yl, 2,4-dichlorotriazin-6-yl and mono-halogeno-sym.-triazinyl radicals, in particular monochloro- and monofluorotriazinyl radicals which are substituted by alkyl, aryl, amino, monoalkylamino, dialkylamino, aralkylamino, arylamino, morpholino, piperidino, pyrrolidino, piperazino, alkoxy, aryloxy, alkylthio or arylthio, where alkyl preferably denotes optionally substituted C1-C4-alkyl, aralkyl preferably denotes optionally substituted phenyl-C1-C4-alkyl and aryl preferably denotes optionally substituted phenyl or naphthyl, and where preferred substituents for alkyl are halogen, hydroxyl, cyano, dialkylamino, morpholino, C1-C4-alkoxy, carboxyl, sulpho or sulphato and preferred substituents for phenyl and naphthyl are sulpho, C1-C4-alkyl, C1-C4-alkoxy, carboxyl, halogen, acylamino, hydroxyl and amino. Radicals which may furthermore be mentioned are 2-amino-4-fluoro-triazin-6-yl, 2-methyl-amino-4-fluorotriazin-6-yl, 2-ethylamino-4-fluorotriazin-6-yl, 2-isopropylamino-4-fluoro-triazin-6-yl, 2-dimethyl-amino-4-fluorotriazin-6-yl, 2-diethylamino-4-fluoro-triazin-6-yl, 2-xcex2-methoxy-ethylamino-4-fluoro-triazin-6-yl, 2-xcex2-hydroxyethylamino-4-fluoro-triazin-6-yl, 2-di-(xcex2-hydroxy-ethylamino)-4-fluoro-triazin-6-yl, 2-carboxy-methylamino-4-fluoro-triazin-6-yl, 2-di-(carboxymethylamino)-4-fluoro-triazin-6-yl, 2-sulphomethyl-methyl-amino-4-fluoro-triazin-6-yl, 2-xcex2-cyanoethylamino-4-fluoro-triazin-6-yl, 2-benzylamino-4-fluoro-triazin-6-yl, 2-xcex2-phenylethylamino-4-fluoro-triazin-6-yl, 2-benzyl-methyl-amino-4-fluoro-triazin-6-yl, 2-(4xe2x80x2-sulphobenzyl)-amino-4-fluoro-triazin-6-yl, 2-cyclohexylamino-4-fluoro-triazin-6-yl, 2-(o-, m-, p-methylphenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m-, p-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2xe2x80x2,5xe2x80x2-disulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m-, p-chlorophenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m-, p-methoxyphenyl)-amino-4-fluoro-triazin-6-yl, 2-(2xe2x80x2-methyl-4xe2x80x2-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2xe2x80x2-methyl-5xe2x80x2-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2xe2x80x2-chloro-4xe2x80x2-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2xe2x80x2-chloro-4xe2x80x2-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2xe2x80x2-methoxy-4xe2x80x2-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m-, p-carboxyphenyl-)-amino-4-fluoro-triazin-6-yl, 2-(2xe2x80x2-,4xe2x80x2-disulphophenyl-)-amino-4-fluoro-triazin-6-yl, 2-(3xe2x80x2-,5xe2x80x2-disulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2xe2x80x2-carboxy-4xe2x80x2-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2xe2x80x2-carboxy-5xe2x80x2-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(6xe2x80x2-sulphonaphth-2xe2x80x2-yl)-amino-4-fluoro-triazin-6-yl, 2-(4xe2x80x2,8xe2x80x2-disulphonaphth-2xe2x80x2-yl)-amino-4-fluoro-triazin-6-yl, 2-(6xe2x80x2,8xe2x80x2-disulphonaphth-2xe2x80x2-yl)-amino-4-fluoro-triazin-6-yl, 2-(N-methyl-N-phenyl)-amino-4-fluoro-triazin-6-yl, 2-(N-ethyl-N-phenyl)-amino-4-fluoro-triazin-6-yl, 2-(N-xcex2-hydroxyethyl-N-phenyl)-amino-4-fluoro-triazin-6-yl, 2-(N-iso-propyl-N-phenyl)-amino-4-fluoro-triazin-6-yl, 2-morpholino-4-fluoro-triazin-6-yl, 2-piperidino-4-fluoro-triazin-6-yl, 2-(4xe2x80x2,6xe2x80x2,8xe2x80x2-trisulphonaphth-2xe2x80x2-yl)-amino-4-fluoro-triazin-6-yl, 2-(3xe2x80x2,6xe2x80x2,8xe2x80x2-trisulphonaphth-2xe2x80x2-yl)-amino-4-fluoro-triazin-6-yl, 2-(3xe2x80x2,6xe2x80x2-disulphonaphth-1xe2x80x2-yl)-amino-4-fluoro-triazin-6-yl, N-methyl-N-(2-methyl-amino-4-chlorotriazin-6-yl)-carbamyl, N-methyl-N-(2-dimethylamino-4-chlorotriazin-6-yl)-carbamyl, N-methyl- or N-ethyl-N-(2,4-dichlorotriazinyl-6)-amino-acetyl, 2-methyloxy-4-fluoro-triazin-6-yl, 2-ethoxy-4-fluoro-triazin-6-yl, 2-phenoxy-4-fluoro-triazin-6-yl, 2-(o-, m- or p-methyl or -methoxy-phenoxy)-4-fluoro-triazin-6-yl, 2-xcex2-hydroxy-ethylmercapto-4-fluoro-triazin-6-yl, 2-phenylmercapto-4-fluoro-triazin-6-yl, 2-(4xe2x80x2-methylphenyl)-mercapto-4-fluorotriazin-6-yl, 2-(2xe2x80x2,4xe2x80x2-dinitrophenyl)-mercapto-4-fluoro-triazin-6-yl, 2-methyl-4-fluoro-triazin-6-yl, 2-phenyl-4-fluoro-triazin-6-yl and the corresponding 4-chloro- and 4-bromo-triazinyl radicals and the corresponding radicals obtainable by replacement of halogen with tertiary bases, such as trimethylamine, triethylamine, dimethyl-xcex2-hydroxyethylamine, triethanolamine, N,N-dimethylhydrazine, pyridine, xcex1-, xcex2- or xcex3-picoline, nicotinic acid or isonicotinic acid, sulphinates, in particular benzenesulphinic acid, or hydrogen sulphite, as well as di- or trihalogenopyrimidine radicals, such as 2,4-dichloropyrimidin-6-yl, 2,4,5-trichloropyrimidin-6-yl, 4,5-dichloropyrimidin-6-yl, 2,4-difluoropyrimidin-6-yl and 4,5-difluoro-5-chloropyrimidyl, as well as 2,3-dichloroquinoxaline-5-carbonyl and 2,3-dichloroquinoxaline-6-carbonyl.
The reactive dyestuffs of the formula (XI) have two possible forms 
Preferred reactive dyestuffs of the formula (XI) are those wherein
KK denotes a bivalent radical of a coupling component of the general formula 
xe2x80x83where the radical (XIIa) or (XIIb) and the azo group are linked to one another via the bond marked with *,
DK denotes a radical of a diazo component of the general formula 
xe2x80x83and
R25=H, C1-C4-alkyl, C1-C4-alkoxy, OH or SO3H,
R26=H, C1-C4-alkyl, C1-C4-alkoxy, ,acylamino, in particular C1-C4-alkylcarbonylamino, C1-C4-alkylsulphonylamino or aminocarbonylamino,
R24 and R27=independently H, CH3, C2H5 or OCH3 and B, R, Y and R1 have the abovementioned meanings.
Reactive dyestuffs according to the invention which are furthermore preferred are those of the formula (XI) or (XIa-(XIb), wherein Y denotes a fibre-reactive fluorine-containing pyrimidin-6-yl radical or a radical of the formula 
wherein
R28 and R29 independently of one another denote H, C1-C4-alkyl and C5-C6-cycloalkyl which are optionally substituted by substituents such as, for example, halogen, cyano, C1-C4-alkoxy, hydroxyl, phenyl, carboxyl, sulpho or sulphato, for example benzyl, phenethyl or cyclohexyl, or C6-C10-aryl, in particular phenyl or naphthyl, which is [lacuna] substituted [lacuna] such as halogen, nitro, cyano, trifluoromethyl, sulphamoyl, carbamoyl, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkanoylamino, benzoylamino, ureido, hydroxyl, carboxyl, sulphomethyl or sulpho,
or wherein R28 and R29, together with the amino nitrogen atom, form a morpholino, piperidino or piperazino radical, and wherein X1=Cl, F or a pyridinium radical which is optionally substituted by, for example, COOH or SO3H.
Particularly preferred reactive dyestuffs are those of the formulae (61)-(72) 
wherein
R0=H, CH3 or ethyl and
R1, R25, R26, B and Y have the abovementioned meaning.
Reactive dyestuffs of the formula (61) to (72) which are particularly preferred above all are those wherein Y is a fluoro-s-triazine radical substituted by xe2x80x94NR28R29 wherein xe2x80x94NR4R5 preferably represents: xe2x80x94NH2, morpholino, N-xcex2-hydroxyethylamino, N,N-di-xcex2-hydroxyethylamino, xcex2-sulphoethylamino, phenylamino, which is optionally substituted on the phenyl nucleus by chlorine, methyl, ethyl, methoxy, ethoxy, acetylamino, hydroxyl, carboxyl, sulphomethyl or sulpho, N-C1-4-alkyl-phenylamino, which is optionally substituted on the phenyl nucleus by chlorine, methyl or ethyl, N-(sulpho-C1-4-alkyl)-phenylamino, which is optionally substituted on the phenyl nucleus by chlorine, methyl or ethyl, N-(hydroxy-C1-4-alkyl)-phenylamino or sulphonaphthylamino.
The invention furthermore relates to a process for the preparation of reactive dyestuffs of the formula (XI), characterized in that dyestuffs of the formula 
are reacted in any desired sequence with in each case one molar equivalent of the reactive component of the formula 
and of the reactive component of the formula
Y-Halxe2x80x83xe2x80x83(VIII)
or in that the corresponding dyestuff precursors of the formulae
R1xe2x80x94NHxe2x80x94[DK]xe2x80x94NH2 and Hxe2x80x94[KK]xe2x80x94NHR
are each reacted with in each case one molar equivalent of the reactive component of the formula (VII) or (VIII) and the products are converted by diazotization and coupling, and if appropriate further conversion reactions, into the reactive dyestuffs of the formula (I), wherein the meaning of the radicals R, R1, R2, Hal, B, p and M corresponds to that given above.
In the preparation of the preferred azo dyestuffs, the diazo component and the coupling component together have two amino groups xe2x80x94N(R0)H and xe2x80x94N(R1)H, and if appropriate other acylatable amino groups. If appropriate, corresponding acetylamino or nitro compounds are used, wherein the acetylamino or nitro group is converted into the NH2 group by hydrolysis or reduction before the condensation with a halogenotriazine, halogenopyrimidine or the like. The reactive radicals B and Y are introduced by condensation of dyestuffs or dyestuff precursors which contain acylatable amino groups with fibre-reactive halogenated acylating agents.
Since the individual process steps described above can be carried out in different sequences, various process variants are possible. In general, the reactions are carried out stepwise in succession, the sequence of the simple reactions between the individual reaction components advantageously depending on the particular conditions.
Since hydrolysis of a halogenotriazine or halogenopyrimidine radical and the like occurs under certain preconditions, an intermediate product which contains acetylamino groups must be hydrolysed in order to split off the acetyl groups before the condensation with an aminodifluorotriazine or trifluorotriazine and the like is carried out. Another possible conversion reaction is, for example, subsequent reaction of a dihalogenotriazinyl radical with an amine. Which reaction is expediently carried out first in the preparation of a secondary condensation product of amine HNR25R29, 2,5,6-trihalogeno-s-triazine and diaminobenzenesulphonic acid, that of the trihalogenotriazine with the amine or with the diaminobenzenesulphonic acid, differs from case to case and depends above all on the solubility of the amino compounds participating and the basicity of the amino groups to be acylated. The most important process variants are described in the embodiment examples.
Suitable starting compounds for the preparation of mono- or polyazo dyestuffs (XI) are, for example:
1,3-Diaminobenzene, 1,4-diaminobenzene, 1,3-diamino-4-methylbenzene, 1,3-diamino-4-ethylbenzene, 1,3-diamino-4-methoxybenzene, 1,3-diamino-4-ethoxybenzene, 1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene, 1,4-diamino-2-ethoxybenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,5-diethylbenzene, 1,4-diamino-2-methyl-5-methoxybenzene, 1,4-diamino-2,5-dimethoxybenzene, 1,4-diamino-2,5-diethoxybenzene, 2,6-diamino-naphthalene, 1,3-diamino-2,4,6-trimethylbenzene, 1,4-diamino-2,3,5,6-tetramethylbenzene, 1,3-diamino-4-nitrobenzene, 4,4xe2x80x2-diaminostilbene, 4,4xe2x80x2-diaminodiphenylmethane, 2,6-diaminonaphthalene-4,8-disulphonic acid, 1,4-diaminobenzene-2-sulphonic acid, 1,4-diaminobenzene-2,5-disulphonic acid, 1,4-diaminobenzene-2,6-disulphonic acid, 1,3-diaminobenzene-4-sulphonic acid, 1,3-diaminobenzene-4,6-disulphonic acid, 1,4-diamino-2-methylbenzene-5-sulphonic acid, 1,5-diamino-6-methylbenzene-3-sulphonic acid, 1,3-diamino-6-methylbenzene-4-sulphonic acid, 3-(3xe2x80x2- or 4xe2x80x2-aminobenzoylamino)-1-aminobenzene-6-sulphonic acid, 1-(4xe2x80x2-aminobenzoylamino)-4-aminobenzene-2,5-disulphonic acid, 1,4-diaminobenzene-2-carboxylic acid, 1,3-diaminobenzene-4-carboxylic acid, 1,2-diaminobenzene-4-carboxylic acid, 1,3-diaminobenzene-5-carboxylic acid, 1,4-diaminobenzene-2-methylbenzene, 4,4xe2x80x2-diaminodiphenyl oxide, 4,4xe2x80x2-diaminodiphenylurea-2,2xe2x80x2-disulphonic acid, 4,4xe2x80x2-diaminodiphenyloxyethane-2,2xe2x80x2-disulphonic acid, 4,4xe2x80x2-diaminostilbene-2,2xe2x80x2-disulphonic acid, 4,4xe2x80x2-diaminodiphenylethane-2,2xe2x80x2-disulphonic acid, 2-amino-5-aminomethylnaphthalene-1-sulphonic acid, 2-amino-5-aminomethylnaphthalene-1,7-disulphonic acid, 1-amino-4-methoxy-5-aminomethylbenzene-6-sulphonic acid, 1-amino-3-(N-methyl)-aminomethylbenzene-6-sulphonic acid, 1-amino-4-(N-methyl)-amino-methylbenzene-3-sulphonic acid, 1-amino-4-aminomethyl-benzene-3-sulphonic acid, 1,3-diaminobenzene-4-(azophenyl-4xe2x80x2-sulphonic acid), 1,3-diaminobenzene-4-(azophenyl-2xe2x80x2,4xe2x80x2-disulphonic acid), 1,3-diaminobenzene-6-sulphonic acid-4-(azophenyl-4xe2x80x2-sulphonic acid), 1,3-diaminobenzene-6-sulphonic acid-4-(azophenyl-3xe2x80x2,6xe2x80x2-disulphonic acid).
If an aminoacetyl compound from which the acetyl group is subsequently split off again by hydrolysis, as is described above in the explanations of the process variants, is to be employed instead of a diamine as the diazo component, the monoacetyl compounds of the above-mentioned diazo components are possible, for example 1-acetylamino-3-aminobenzene-4-sulphonic acid or 1-acetylamino-4-aminobenzene-3-sulphonic acid.
1-Amino-8-hydroxynaphthalene-6-sulphonic acid, 1-amino-8-hydroxynaphthalene-2,4-disulphonic acid, 2-hydroxy-3-aminonaphthalene-5,7-disulphonic acid, 1-amino-8-hydroxynaphthalene-2,4,6-trisulphonic acid, 1-hydroxy-8-acetyl-aminonaphthalene-3-sulphonic acid, 2-amino-5-hydroxynaphthalene-7-sulphonic acid, 2-methyl- or 2-ethylamino-5-hydroxynaphthalene-7-sulphonic acid, 2-(N-acetyl-N-methylamino)-5-hydroxynaphthalene-7-sulphonic acid, 2-acetylamino-5-hydroxynaphthalene-7-sulphonic acid, 2-amino-5-hydroxynaphthalene-1,7-disulphonic acid, 2-amino-8-hydroxynaphthalene-6-sulphonic acid, 2-(N-acetyl-N-methylamino)-8-hydroxynaphthalene-6-sulphonic acid, 2-acetylamino-8-hydroxynaphthalene-6-sulphonic acid, 2-amino-8-hydroxynaphthalene-3,6-disulphonic acid, 2-acetylamino-8-hydroxynaphthalene-3,6-disulphonic acid, 1-amino-5-hydroxynaphthalene-7-sulphonic acid, 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid, 1-acetylamino-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid, 1-(4xe2x80x2-aminobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid, 1-(4xe2x80x2-nitrobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid, 1-(3xe2x80x2-aminobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid, 1-(3xe2x80x2-nitrobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid, 1-amino-8-hydroxynaphthalene-4-sulphonic acid.
The diazotization of the diazo components or of the intermediate products containing a diazotizable amino group is as a rule carried out by the action of nitrous acid in aqueous-mineral acid solution at a low temperature. The coupling to the coupling components is carried out at weakly acid, neutral to weakly alkaline pH values.
The condensation of the reactive components with the diazo components and the coupling components and with the amines or with acylatable monoazo or diazo intermediate products or with the dyestuffs containing amino groups is preferably carried out in aqueous solution or suspension at a low temperature and at a weakly acid, neutral to weakly alkaline pH value. Preferably, the hydrogen halide liberated during the condensation is neutralized continuously by addition of aqueous alkali metal hydroxides, bicarbonates or carbonates.
The formulae shown are those of the free acids. In general, the salts, in particular the alkali metal salts, such as sodium, potassium or lithium salts, are obtained in the preparation. The charge formed by quaternization with pyridines is compensated by a counterion, for example chloride, fluorine or sulphate, depending on the isolation conditions; or the dyestuffs form inert salts with sulpho or carboxyl groups. The dyestuffs can also be employed as concentrated solutions.
The reactive dyestuffs of the formula (I) are suitable for dyeing and printing naturally occurring or synthetic materials containing hydroxyl groups or amide groups, such as silk, leather, wool and synthetic polyamide fibres, but in particular cellulose-containing materials having a fibrous structure, such as linen, cellulose, regenerated cellulose and above all cotton. They are suitable both for the exhaust process and for dyeing by the customary pad-dyeing processes, in which the goods are impregnated with aqueous and if appropriate also salt-containing dyestuff solutions and the dyestuffs are fixed after treatment with alkali or in the presence of alkali, if appropriate under the action of heat.
The reactive dyestuffs of the formula (I) are distinguished by a high reactivity and excellent fixing capacity. Because of their trifunctionality, they also give high fixing yields from a long liquor. They are characterized by the yield being relatively independent of the dyeing temperature, and can therefore be employed in the exhaust process at low to moderate dyeing temperatures. In the pad-steam process, they require only short steaming times. They produce dyeings of good colour strength with good light- and wet-fastnesses.
The invention furthermore relates to textile products comprising materials containing hydroxyl groups or amide groups which have been dyed with dyestuffs of the formula (I).